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Title: Activation of Low-Valent, Multiply M–M Bonded Group VI Dimers toward Catalytic Olefin Metathesis via Surface Organometallic Chemistry

Abstract

Olefin metathesis is a broadly employed reaction with applications that range from fine chemicals to materials and petrochemicals. The design and investigation of olefin metathesis catalysts have been ongoing for over half a century, with advancements made in terms of activity, stability, and selectivity. Immobilization of organometallic complexes onto solid supports such as silica or alumina is a promising strategy for catalyst heterogenization, often resulting in increased activity and stability. Consequently, a broad range of early transition metal catalysts bearing alkyl, oxide/alkoxide, and amide ligands have been grafted onto silica and their reactivities investigated. In this paper, we report a series of silica-supported tungsten and molybdenum dimers (X3M≡MX3, where M = W and Mo; X = neopentyl, tert-butoxide, and dimethyl amide) and their reactivities toward catalytic olefin metathesis. Dynamic nuclear polarization (DNP)-enhanced solid-state nuclear magnetic resonance (SSNMR), diffuse reflectance infrared Fourier transform (DRIFT), UV resonance Raman, and X-ray absorption (XAS) spectroscopies suggest that upon heterogenization the dimers bind to the surface in a monopodal fashion, with the M≡M triple bond remaining intact. These structural assignments were further corroborated by density functional theory (DFT) calculations. While the homogeneous dimer counterparts are inert, the supported low-valent alkyl W and Mo dimers becomemore » active for the disproportionative self-metathesis of propylene to ethylene and butenes and 4-nonene to 4-octene and 5-decene under mild conditions. The lack of activity observed for the free and supported tert-butoxide and dimethyl amide dimers likely suggests that the neopentyl groups are necessary for the formation of a putative alkylidene active species. The difference in reactivity between the free and supported dimers could be explained either by the lowering of the activation barrier of the complex through the electronic effects of the surface or by site isolation of catalytically relevant reactive intermediates.« less

Authors:
 [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [2];  [1];  [1]; ORCiD logo [3]; ORCiD logo [1]; ORCiD logo [4];  [5]; ORCiD logo [5];  [5];  [1];  [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division
  2. Ames Lab., Ames, IA (United States)
  3. Argonne National Lab. (ANL), Argonne, IL (United States). Chemical Sciences and Engineering Division; ; Northwestern Univ., Evanston, IL (United States). Center for Catalysis and Surface Science
  4. Argonne National Lab. (ANL), Argonne, IL (United States). Center for Nanoscale Materials
  5. Univ. of Minnesota, Minneapolis, MN (United States)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Energy Frontier Research Center for Inorganometallic Catalyst Design (ICDC); Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Vehicle Technologies Office
OSTI Identifier:
1632171
Grant/Contract Number:  
AC02-06CH11357; AC02-07CH11358; SC0012702; FG02-03ER15457
Resource Type:
Accepted Manuscript
Journal Name:
Organometallics
Additional Journal Information:
Journal Volume: 39; Journal Issue: 7; Journal ID: ISSN 0276-7333
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Group VI dimers; Olefin metathesis; alkylidene; bimetallic; propylene

Citation Formats

Chapovetsky, Alon, Langeslay, Ryan R., Celik, Gokhan, Perras, Frédéric A., Pruski, Marek, Ferrandon, Magali S., Wegener, Evan C., Kim, Hacksung, Dogan, Fulya, Wen, Jianguo, Khetrapal, Navneet, Sharma, Prachi, White, Jacob, Kropf, A. Jeremy, Sattelberger, Alfred P., Kaphan, David M., and Delferro, Massimiliano. Activation of Low-Valent, Multiply M–M Bonded Group VI Dimers toward Catalytic Olefin Metathesis via Surface Organometallic Chemistry. United States: N. p., 2020. Web. https://doi.org/10.1021/acs.organomet.9b00787.
Chapovetsky, Alon, Langeslay, Ryan R., Celik, Gokhan, Perras, Frédéric A., Pruski, Marek, Ferrandon, Magali S., Wegener, Evan C., Kim, Hacksung, Dogan, Fulya, Wen, Jianguo, Khetrapal, Navneet, Sharma, Prachi, White, Jacob, Kropf, A. Jeremy, Sattelberger, Alfred P., Kaphan, David M., & Delferro, Massimiliano. Activation of Low-Valent, Multiply M–M Bonded Group VI Dimers toward Catalytic Olefin Metathesis via Surface Organometallic Chemistry. United States. https://doi.org/10.1021/acs.organomet.9b00787
Chapovetsky, Alon, Langeslay, Ryan R., Celik, Gokhan, Perras, Frédéric A., Pruski, Marek, Ferrandon, Magali S., Wegener, Evan C., Kim, Hacksung, Dogan, Fulya, Wen, Jianguo, Khetrapal, Navneet, Sharma, Prachi, White, Jacob, Kropf, A. Jeremy, Sattelberger, Alfred P., Kaphan, David M., and Delferro, Massimiliano. Thu . "Activation of Low-Valent, Multiply M–M Bonded Group VI Dimers toward Catalytic Olefin Metathesis via Surface Organometallic Chemistry". United States. https://doi.org/10.1021/acs.organomet.9b00787. https://www.osti.gov/servlets/purl/1632171.
@article{osti_1632171,
title = {Activation of Low-Valent, Multiply M–M Bonded Group VI Dimers toward Catalytic Olefin Metathesis via Surface Organometallic Chemistry},
author = {Chapovetsky, Alon and Langeslay, Ryan R. and Celik, Gokhan and Perras, Frédéric A. and Pruski, Marek and Ferrandon, Magali S. and Wegener, Evan C. and Kim, Hacksung and Dogan, Fulya and Wen, Jianguo and Khetrapal, Navneet and Sharma, Prachi and White, Jacob and Kropf, A. Jeremy and Sattelberger, Alfred P. and Kaphan, David M. and Delferro, Massimiliano},
abstractNote = {Olefin metathesis is a broadly employed reaction with applications that range from fine chemicals to materials and petrochemicals. The design and investigation of olefin metathesis catalysts have been ongoing for over half a century, with advancements made in terms of activity, stability, and selectivity. Immobilization of organometallic complexes onto solid supports such as silica or alumina is a promising strategy for catalyst heterogenization, often resulting in increased activity and stability. Consequently, a broad range of early transition metal catalysts bearing alkyl, oxide/alkoxide, and amide ligands have been grafted onto silica and their reactivities investigated. In this paper, we report a series of silica-supported tungsten and molybdenum dimers (X3M≡MX3, where M = W and Mo; X = neopentyl, tert-butoxide, and dimethyl amide) and their reactivities toward catalytic olefin metathesis. Dynamic nuclear polarization (DNP)-enhanced solid-state nuclear magnetic resonance (SSNMR), diffuse reflectance infrared Fourier transform (DRIFT), UV resonance Raman, and X-ray absorption (XAS) spectroscopies suggest that upon heterogenization the dimers bind to the surface in a monopodal fashion, with the M≡M triple bond remaining intact. These structural assignments were further corroborated by density functional theory (DFT) calculations. While the homogeneous dimer counterparts are inert, the supported low-valent alkyl W and Mo dimers become active for the disproportionative self-metathesis of propylene to ethylene and butenes and 4-nonene to 4-octene and 5-decene under mild conditions. The lack of activity observed for the free and supported tert-butoxide and dimethyl amide dimers likely suggests that the neopentyl groups are necessary for the formation of a putative alkylidene active species. The difference in reactivity between the free and supported dimers could be explained either by the lowering of the activation barrier of the complex through the electronic effects of the surface or by site isolation of catalytically relevant reactive intermediates.},
doi = {10.1021/acs.organomet.9b00787},
journal = {Organometallics},
number = 7,
volume = 39,
place = {United States},
year = {2020},
month = {2}
}

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